Phenylazobenzenes or naphthylazobenzenes having a plurality of fiber-reactive groups

ABSTRACT

Reactive dyes of the formula ##STR1## where n is 0 or 1, 
     R 1 , R 2  and R 3  are each hydrogen, C 1  -C 4  -alkyl or phenyl, 
     A is unsubstituted or substituted C 2  -C 8  -alkylene, 
     Y is vinyl or a radical of the formula --CH 2  --CH 2  --Q, where 
     Q is a group which can be eliminated under alkaline reaction conditions, 
     D 1  is phenyl or naphthyl, where these radicals may be substituted, 
     D 2  is phenylene or naphthylene, where these radicals may be substituted, and 
     Z is a reactive radical, 
     with the proviso that 
     a) n is zero when D 1  is substituted by unsubstituted or substituted phenylazo or by unsubstituted or substituted naphthylazo and 
     b) the reactive radical Z is not devised from the triazine series when n is zero and D 1  is dihydroxysulfonylphenyl or trihydroxysulfonylnaphthyl, 
     are used for dyeing and printing organic substrates containing hydroxyl groups or nitrogen atoms.

The present invention relates to novel reactive dyes of the formula I ##STR2## where n is 0 or 1,

R¹, R² and R³ are identical or different and, independently of one another, are each hydrogen, C₁ -C₄ -alkyl or phenyl,

A is C₂ -C₈ -alkylene which may be interrupted by from 1 to 3 oxygen atoms, imino groups or C₁ -C₄ -alkylimino groups,

Y is vinyl or a radical of the formula --CH₂ --CH₂ --Q, where

Q is a group which can be eliminated under alkaline reaction conditions,

D¹ is phenyl or naphthyl, where these radicals may be monosubstituted or polysubstituted by hydroxysulfonyl, carboxyl, C₁ -C₄ -alkoxycarbonyl, cyano, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, halogen, nitro or vinylsulfonyl or monosubstituted by unsubstituted or substituted phenylazo or by unsubstituted or substituted naphthylazo,

D¹ is unsubstituted or substituted phenylene or unsubstituted or substituted naphthylene and

Z is a reactive radical,

with the proviso that

a) n is zero when D¹ is substituted by unsubstituted or substituted phenylazo or by unsubstituted or substituted naphthylazo, and

b) the reactive radical Z is not derived from the triazine series when n is zero and D¹ is dihydroxysulfonylphenyl or trihydroxysulfonylnaphthyl,

and the use of the novel dyes for dyeing or printing fibers having hydroxyl groups or nitrogen atoms.

EP-A No. 174 909 discloses reactive dyes which contain the vinylsulfonyl radical as a reactive group, this radical being bonded to the dye radical via the ureido group.

Dyes of the formula I where n is zero, D¹ is dihydroxysulfonylphenyl or trihydroxysulfonylnaphthyl and Z is a reactive radical from the triazine series are described in the prior Patent Application EP-A No. 437 669.

It is an object of the present invention to provide novel reactive dyes which likewise have a vinyl-sulfonyl group which is bonded to the chromophore via a ureido group, and the novel dyes should have advantageous performance characteristics.

We have found that this object is achieved by the reactive dyes of the formula I which were defined at the outset.

All alkyl and alkylene groups occurring in the abovementioned formula I may be both straight-chain and branched.

R¹, R² and R³ are, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl or sec-butyl.

A is, for example, --(CH₂)₂ --, --(CH₂)₃ --, --(CH₂)₄ --, CH₂)₅ --, --(CH₂)₆ --, --(CH₂)₇ --, --(CH₂)₈ --, --CH(CH₃)--CH₂ --, --CH(CH₃)--CH(CH₃)--(CH₂)₂ --O--(CH₂)₂ --, --(CH₂)₂ --NH--(CH₂)₂, .sub.(CH₂)₂ --N(CH₃)--(CH₂)₂ --, --(CH₂)₂ --O--(CH₂)₂ --O--(CH₂)₂ -- or --(CH₂ O--(CH₂)₂ --O--(CH₂)₂ --O--(CH₂)₂ --.

In formula I, Y is, inter alia, a group which can be eliminated under alkaline reaction conditions. Examples of such groups are chlorine, OSO₃ H, SSO₃ H, OP(O)(OH)₂, C₁ -C₄ -alkylsulfonyloxy, phenylsulfonyloxy, C₁ -C₄ -alkanoyloxy, C₁ -C₄ -dialkylamino, ##STR3## where Q¹, Q² and Q³ are identical or different and, independently of one another, are each C₁ -C₄ -alkyl or benzyl and An.sup.⊖ in each case is an anion. (Examples of suitable anions are fluoride, chloride, bromide, iodide, mono-, di- or trichloroacetate, methanesulfonate, benzenesulfonate or 2- or 4-methylbenzenesulfonate.)

When D¹ is phenyl or naphthyl which is monosubstituted by substituted phenylazo or substituted naphthylazo, or when D² is substituted phenylene or substituted naphthylene, suitable substituents f or this purpose are hydroxysulfonyl or the radical --NR² --CO--NR³ --A--SO₂ --Y, where R², R³, A and Y each have the abovementioned meaning. The phenyl nuclei are as a rule monosubstituted or disubstituted by hydroxysulfonyl or monosubstituted by the radical --NR² --CO--NR³ --A--SO₂ --A, and the naphthyl nuclei are monosubstituted to trisubstituted by hydroxysulfonyl or monosubstituted by the radical --NR² --CO--NR³ --A--SO₂ --Y.

D¹ is, for example, 2,4-dihydroxysulfonylphenyl, 2,5-dihydroxysulfonylphenyl, 2,5-dihydroxysulfonyl-4-methylphenyl, 2,5-dihydroxysulfonyl-6-chlorophenyl, 3,6,8-trihydroxysulfonylnaphth-2-yl, 4,6,8-trihydroxysulfonylnaphth-2-yl, 1,5-dihydroxysulfonylnaphth-2-yl or 1,6-dihydroxysulfonylnaphth-2-yl.

Reactive radicals Z are derived, for example, from the heterocyclic or the aliphatic series.

Suitable reactive radicals Z are, for example, of the formula ##STR4## where R⁴ is C₁ -C₄ -alkoxy, phenoxy or a radical of the formula NL¹ L² where L¹ and L² are identical or different and, independently of one another, are each C₁ -C₄ -alkyl, which is unsubstituted or substituted by hydroxyl, hydroxysulfonyl or sulfato, or unsubstituted or substituted phenyl, or L¹ and L², together with the nitrogen atom binding them, form a 5-membered or 6-membered saturated heterocyclic radical which may contain further hetero atoms, or L¹ is also hydrogen,

R⁵ is fluorine, chlorine, bromine, C₁ -C₄ -alkylsulfonyl, phenylsulfonyl or a radical of the formula ##STR5## and R⁶ is a radical of the formula --OCH₂ CCl₃, --OCH₂ --CBr═CH₂, --OCH₂ --CCl═CHCl, --OCH₂ --C.tbd.CH, --OC₂ H₄ --N.sup.⊕ (CH₃)₃ Cl.sup.⊖ or --SCH₂ --COOH

and Y has the abovementioned meanings.

If substituted phenyl radicals occur in R⁴, examples of suitable substituents are C₁ -C₄ -alkyll C₁ -C₄ -haloalkyl, C₁ -C₄ -alkoxy, C-imino, C₁ -C₄ -mono- or dialkylamino, nitro, formyl, cyano, carboxyl or hydroxysulfonyl.

R⁴ is, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, mono- or dimethylamino, mono- or diethylamino, mono- or dipropylamino, mono- or diisopropylamino, mono- or dibutylamino, N-methyl-N-ethylamino, N-(2-hydroxyethyl)-amino, N-(2-hydroxysulfonylethyl)-amino, N-(2-sulfatoethyl)-amino, mono- or diphenylamino, N-methyl-N-phenylamino, N-ethyl-N-phenylamino, N-propyl-N-phenylamino, N-isopropyl-N-phenylamino, N-butyl-N-phenylamino, 2- or 4-methylphenylamino, N-methyl-N-(2- or 4-methylphenyl)-amino, N-ethyl-N-(2- or 4-methylphenyl)-amino, 2- or 4-chloromethylphenylamino, N-methyl-N-(2- or 4-chloromethylphenyl)amino, N-ethyl-N-(2- or 4-chloromethylphenyl)-amino, 2- or 4-trifluoromethylphenylamino, N-methyl-N-(2- or 4-trifluoromethylphenyl)-amino, N-ethyl-N-(2- or 4-trifluoromethylphenyl)-amino, 2-methoxyphenylamino, N-methyl-N-(2-methoxyphenyl)-amino, N-ethyl-N-(2-methoxyphenyl)-amino, 2-aminophenylamino, N-methyl-N-(2-aminophenyl)-amino, N-ethyl-N- (2-aminophenyl) -amino, 2-methylaminophenylamino, N-methyl-N-(2-methylaminophenyl)-amino, N-ethyl-N-(2-methylaminophenyl)-amino, 2-dimethylaminophenylamino, N-methyl-N- (2-dimethylaminophenyl) -amino, N-ethyl-N-(2-dimethylaminophenyl)-amino, 3-nitrophenylamino, N-methyl-N-(3-nitrophenyl)-amino, N-ethyl-N-(3-nitrophenyl)-amino, 3-cyanophenylamino, N-methyl-N-(3-cyanophenyl)-amino, N-ethyl-N-(3-cyanophenyl)-amino, 3-formylphenylamino, N-methyl-N-(3-formylphenyl)-amino, N-ethyl-N-(3-formylphenyl)-amino, 3-carboxyphenylamino, N-methyl-N-(3-carboxyphenyl)-amino, N-ethyl-N-(3-carboxyphenyl)-amino, 3-hydroxysulfonylphenylamino, N-methyl-N-(3-hydroxysulfonylphenyl)-amino, N-ethyl-N-(3-hydroxysulfonylphenyl)-amino, pyrrolidino, piperidino, morpholino, piperazino or N-(C₁ -C₄ -alkyl)-piperazino.

R⁵ is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl or butysulfonyl.

Preferred reactive dyes of the formula I are those in which

n is zero,

R¹, R² and R³ are each hydrogen,

A is C₂ -C₄ -alkylene which may be interrupted by an oxygen atom and

D¹ is phenyl or naphthyl, where these radicals are mono-substituted to trisubstituted by hydroxysulfonyl.

Other preferred reactive dyes of the formula I are those in which Z is a radical from the pyrazine, pyrimidine, quinoxaline, triazine, vinylsulfonyl or acryloyl series.

When n is 1 or when D¹ is not dihydroxysulfonyl or trihydroxysulfonylnaphthyl, particularly noteworthy reactive dyes of the formula I are those in which Z is a radical of the formula ##STR6## where R⁴ and R⁵ each have the abovementioned meanings. In particular, the following dyes may be mentioned, in which R⁴ is a radical of the formula NL¹ L², where L¹ is C₁ -C₄ alkyl and L² is substituted phenyl or in particular unsubstituted phenyl, and R⁵ is fluorine or chlorine.

Particularly preferred reactive dyes of the formula I are those in which D¹ is dihydroxysulfonylphenyl or trihydroxysulfonylnaphthyl.

The novel reactive dyes of the formula I (where n is 0) are obtained in an advantageous manner if, for example, an amine of the formula II

    D.sup.1 --NH.sub.2                                         (II)

where D¹ has the abovementioned meanings, is diazotized in a conventional manner and the product is coupled to a phenylenediamine of the formula III ##STR7## where R¹, R², R³ and A each have the abovementioned meaning and Y¹ is 2-hydroxyethyl or the radical Y.

The resulting azo dye of the formula IV ##STR8## where D¹, R¹, R², R³, A and Y¹ each have the abovementioned meanings, can then be reacted in a known manner with a compound of the formula V

    Hal--Z                                                     (V)

where Z has the abovementioned meanings and Hal is fluorine or chlorine.

The novel reactive dyes of the formula I where n is 1 can be prepared, for example, by diazotizing an azo dye of the formula IVa ##STR9## where D¹, R², R³ A and Y¹ each have the abovementioned meanings, which dye can be obtained as described above, and coupling the product to an amine derivative of the formula VI

    H--D.sup.2 --NH--R.sup.1                                   (VI)

where R¹ and D² each have the abovementioned meanings, and reacting the product, as described above, with a compound of the formula V.

The phenylenediamines of the formula III are prepared in a conventional manner, as described in, for example, the prior Patent Application EP-A No. 437 669 or in the prior German Patent Application P 41 07 692.3.

Where Y¹ is 2-hydroxyethyl, the latter is finally converted into the radical Y, likewise in a conventional manner, for example by esterification with sulfuric acid.

The novel reactive dyes of the formula I can advantageously be used for dyeing or printing organic substrates having hydroxyl groups or nitrogen atoms. Examples of such substrates are leather or fiber material which contains predominantly natural or synthetic polyamides or natural or regenerated cellulose. The novel dyes are preferably used for dyeing and printing textile material based on cotton. The novel reactive dyes can also be employed for discharge printing since they can be discharged under alkaline conditions.

The Examples which follow illustrate the invention.

The phenylenediamines used therein as coupling components are described in the prior Patent Application EP-A No. 437 669 under Examples 5 to 8, and in the prior German Patent Application P 41 07 692.3, under Examples Z4 to Z9.

EXAMPLE 1

101.2 g (0.4 mol) of aniline-2,4-disulfonic acid were diazotized in 400 ml of water containing hydrochloric acid, and the product was added to a suspension of 132 g (0.4 mol) of the compound of the formula ##STR10## in 500 ml of water. The coupling reaction was carried out at from 0° to 50° C. and at a pH of 3 by adding 2 N potassium bicarbonate solution. The reaction solution described above was subjected to a condensation reaction with 88 g (0.4 mol) of tetrachloropyrimidine at from 30° to 450° C. and at a pH of from 6 to 7. The solution was then clarified by filtration and the reactive dye was isolated by salting out. It is of the formula (free acid) ##STR11## and dyes cotton in a yellow hue with good lightfastness and fastness to wet treatments.

The dyes of the formula ##STR12## which are described in Table 1 can be obtained in a similar manner.

                  TABLE 1                                                          ______________________________________                                         Ex.                                    Hue on                                  no.  D                     E      m    cotton                                  ______________________________________                                          2                                                                                   ##STR13##            H      2    yellow                                   3                                                                                   ##STR14##            H      3    yellow                                   4                                                                                   ##STR15##            CH.sub.3                                                                              2    yellow                                   5                                                                                   ##STR16##            H      3    yellow                                   6                                                                                   ##STR17##            CH.sub.3                                                                              2    yellow                                   7                                                                                   ##STR18##            H      2    yellow                                   8                                                                                   ##STR19##            H      3    yellow                                   9                                                                                   ##STR20##            CH.sub.3                                                                              2    yellow                                  10                                                                                   ##STR21##            H      2    reddish yellow                          11                                                                                   ##STR22##            H      3    reddish yellow                          12                                                                                   ##STR23##            CH.sub.3                                                                              2    reddish yellow                          13                                                                                   ##STR24##            CH.sub.3                                                                              2    reddish yellow                          14                                                                                   ##STR25##            H      3    reddish yellow                          15                                                                                   ##STR26##            CH.sub.3                                                                              2    reddish yellow                          16                                                                                   ##STR27##            H      2    yellow                                  17                                                                                   ##STR28##            H      3    yellow                                  18                                                                                   ##STR29##            CH.sub.3                                                                              2    yellow                                  19                                                                                   ##STR30##            H      2    yellow                                  20                                                                                   ##STR31##            H      3    yellow                                  21                                                                                   ##STR32##            CH.sub.3                                                                              2    yellow                                  ______________________________________                                    

EXAMPLE 22

101.2 g (0.4 mol) of aniline-2,5-disulfonic acid were diazotized in 400 ml of water containing hydrochloric acid, and the product was added to a suspension of 132 g (0.4 mol) of the compound of the formula ##STR33## in 500 ml of water. The coupling reaction was carried out at from 0° to 5° C. and at a pH of 3 by means of 2 N potassium bicarbonate solution. The reaction solution described above was subjected to a condensation reaction with 67.4 g (0.4 mol) of 2,4,6-trifluoro-5-chloropyrimidine at from 0° to 50° C. and at a pH of from 6 to 7. The solution was then clarified by filtration and the reactive dye was isolated by spray drying. It is of the formula (free acid) ##STR34## and dyes cotton in a yellow hue with good lightfastness and fastness to wet treatments.

The dyes of the formula ##STR35## which are described in Table 2 can be obtained in a similar manner.

                                      TABLE 2                                      __________________________________________________________________________     Ex. no.                                                                            D                 E  m Y       Hue on cotton                               __________________________________________________________________________     23                                                                                  ##STR36##        H  2 C.sub.2 H.sub.4 OCOCH.sub.3                                                            yellow                                      24                                                                                  ##STR37##        CH.sub.3                                                                          2 C.sub.2 H.sub.4 OCOCH.sub.3                                                            yellow                                      25                                                                                  ##STR38##        H  3 C.sub.2 H.sub.4 OCOCH.sub.3                                                            yellow                                      26                                                                                  ##STR39##        H  3 C.sub.2 H.sub.4 OCOCH.sub.3                                                            yellow                                      27                                                                                  ##STR40##        CH.sub.3                                                                          2 C.sub.2 H.sub.4 OCOCH.sub.3                                                            yellow                                      28                                                                                  ##STR41##        H  2 CHCH.sub.2                                                                             yellow                                      29                                                                                  ##STR42##        H  2 CHCH.sub.2                                                                             yellow                                      30                                                                                  ##STR43##        H  2 C.sub.2 H.sub.4 Cl                                                                     yellow                                      31                                                                                  ##STR44##        H  2 C.sub.2 H.sub.4 Cl                                                                     yellow                                      32                                                                                  ##STR45##        H  2 C.sub.2 H.sub.4 OCOCH.sub.3                                                            yellow                                      33                                                                                  ##STR46##        H  2 CHCH.sub.2                                                                             yellow                                      34                                                                                  ##STR47##        H  2 C.sub.2 H.sub.4 Cl                                                                     yellow                                      35                                                                                  ##STR48##        H  2 C.sub.2 H.sub.4 OCOCH.sub.3                                                            yellow                                      36                                                                                  ##STR49##        H  2 C.sub.2 H.sub.4 Cl                                                                     yellow                                      37                                                                                  ##STR50##        H  2 CHCH.sub.2                                                                             yellow                                      38                                                                                  ##STR51##        H  2 C.sub.2 H.sub.4 OCOCH.sub.3                                                            yellow                                      39                                                                                  ##STR52##        H  2 CHCH.sub.2                                                                             yellow                                      40                                                                                  ##STR53##        H  2 C.sub.2 H.sub.4 Cl                                                                     yellow                                      41                                                                                  ##STR54##        H  2 C.sub.2 H.sub.4 OCOCH.sub.3                                                            yellow                                      42                                                                                  ##STR55##        H  2 CHCH    yellow                                      43                                                                                  ##STR56##        H  2 C.sub.2 H.sub.4 Cl                                                                     yellow                                      44                                                                                  ##STR57##        H  2 C.sub.2 H.sub.4 OCOCH.sub.3                                                            yellow                                      45                                                                                  ##STR58##        H  2 CHCH    yellow                                      46                                                                                  ##STR59##        H  2 C.sub.2 H.sub.4 Cl                                                                     yellow                                      __________________________________________________________________________

EXAMPLE 47

0.5 mol of the coupling solution described in Example 1 was subjected to a condensation reaction with 91.8 g (0.5 mol) of 2,4,6-trichloropyrimidine at from 40° to 60° C. and at a pH of from 6 to 7. The resulting reaction solution was clarified by filtration and the reactive dye was isolated by salting out. It is of the formula (free acid) ##STR60## and dyes cotton in a yellow hue.

The dyes of the formula ##STR61## which are shown in Table 3 were obtained in a similar manner.

                                      TABLE 3                                      __________________________________________________________________________     Ex. no.                                                                            D                 E  m Y       Hue on cotton                               __________________________________________________________________________     48                                                                                  ##STR62##        H  2 C.sub.2 H.sub.4 OCOCH.sub.3                                                            yellow                                      49                                                                                  ##STR63##        H  2 C.sub.2 H.sub.4 OCOCH.sub.3                                                            yellow                                      50                                                                                  ##STR64##        CH.sub.3                                                                          2 C.sub.2 H.sub.4 Cl                                                                     yellow                                      51                                                                                  ##STR65##        H  3 C.sub.2 H.sub.4 OCOCH.sub.3                                                            yellow                                      52                                                                                  ##STR66##        H  2 CHCH.sub.2                                                                             yellow                                      53                                                                                  ##STR67##        CH.sub.3                                                                          2 C.sub.2 H.sub.4 Cl                                                                     yellow                                      __________________________________________________________________________

EXAMPLE 54

191.5 g (0.5 mol) of 2-aminonaphthalene-3,6,8-trisulfonic acid were diazotized in 500 ml of water containing hydrochloric acid and the product was added to a suspension of 164.5 g (0.5 mol) of the compound of the formula ##STR68## in 600 ml of water. The coupling reaction was carried out at from 0° to 50° C. and at a pH of from 2 to 3. The resulting reaction solution was subjected to a condensation reaction with 127.8 g (0.5 mol) of 4,5-dichloro-1-(2-chlorocarbonylethyl)-pyridaz-6-one at from 20° to 30° C. and at a pH of from 6 to 7. The resulting dye solution was clarified by filtration and the reactive dye of the formula (free acid) ##STR69## was isolated by spray drying. It dyes cotton in a yellow hue with good lightfastness and fastness to wet treatments.

The dyes of the formula ##STR70## which are shown in Table 4 can be obtained in a similar manner.

                                      TABLE 4                                      __________________________________________________________________________     Ex. no.                                                                            D                 E  m Y       Hue on cotton                               __________________________________________________________________________     55                                                                                  ##STR71##        CH.sub.3                                                                          2 C.sub.2 H.sub.4 OCOCH.sub.3                                                            yellow                                      56                                                                                  ##STR72##        H  3 C.sub.2 H.sub.4 OCOCH.sub.3                                                            yellow                                      57                                                                                  ##STR73##        H  2 C.sub.2 H.sub.4 OCOCH.sub.3                                                            yellow                                      58                                                                                  ##STR74##        H  2 C.sub.2 H.sub.4 Cl                                                                     yellow                                      59                                                                                  ##STR75##        H  2 CHCH.sub.2                                                                             yellow                                      60                                                                                  ##STR76##        H  2 C.sub.2 H.sub.4 OCOCH.sub.3                                                            yellow                                      61                                                                                  ##STR77##        H  2 C.sub.2 H.sub.4 OCOCH.sub.3                                                            yellow                                      62                                                                                  ##STR78##        H  2 C.sub.2 H.sub.4 OCOCH.sub.3                                                            yellow                                      63                                                                                  ##STR79##        H  2 C.sub.2 H.sub.4 Cl                                                                     yellow                                      64                                                                                  ##STR80##        H  2 C.sub.2 H.sub.4 OCOCH.sub.3                                                            yellow                                      65                                                                                  ##STR81##        H  2 CHCH.sub.2                                                                             yellow                                      66                                                                                  ##STR82##        H  2 C.sub.2 H.sub.4 OCOCH.sub. 3                                                           yellow                                      67                                                                                  ##STR83##        H  2 C.sub.2 H.sub.4 OCOCH.sub.3                                                            yellow                                      68                                                                                  ##STR84##        H  3 C.sub.2 H.sub.4 OCOCH.sub.3                                                            yellow                                      69                                                                                  ##STR85##        CH.sub.3                                                                          2 C.sub.2 H.sub.4 OCOCH.sub.3                                                            yellow                                      __________________________________________________________________________

EXAMPLE 70

126.5 g (0.5 mol) of aniline-2,4-disulfonic acid were diaiotized in 500 ml of water containing hydrochloric acid, and the product was added to a suspension of 164.5 g (0.5 mol) of the compound of the formula ##STR86## in 500 ml of water. The coupling reaction was carried out at from 0° to 50° C. and at a pH of 3. This reaction solution was subjected to a condensation reaction with 130.8 g (0.5 mol) of 2,3-dichloroquinoxaline-6-carbonyl chloride at from 20° to 35° C. and at a pH of from 6 to 7. The resulting dye solution was clarified by filtration and the reactive dye of the formula (free acid) ##STR87## was isolated by spray drying. It dyes cotton in a yellow hue.

The dyes of the formula ##STR88## which are shown in Table 5 can be obtained in a similar manner.

                                      TABLE 5                                      __________________________________________________________________________     Ex. no.                                                                            D                 E  m Y       Hue on cotton                               __________________________________________________________________________     71                                                                                  ##STR89##        H  2 CHCH.sub.2                                                                             yellow                                      72                                                                                  ##STR90##        CH.sub.3                                                                          2 C.sub.2 H.sub.4 OCOCH.sub.3                                                            yellow                                      73                                                                                  ##STR91##        H  2 C.sub.2 H.sub.4 OCOCH.sub.3                                                            yellow                                      74                                                                                  ##STR92##        H  2 C.sub.2 H.sub.4 Cl                                                                     yellow                                      75                                                                                  ##STR93##        H  2 C.sub.2 H.sub.4 OCOCH.sub.3                                                            yellow                                      76                                                                                  ##STR94##        CH.sub.3                                                                          2 C.sub.2 H.sub.4 OCOCH.sub.3                                                            yellow                                      77                                                                                  ##STR95##        H  2 CHCH.sub.2                                                                             yellow                                      78                                                                                  ##STR96##        H  3 C.sub.2 H.sub.4 OCOCH.sub.3                                                            yellow                                      79                                                                                  ##STR97##        H  2 C.sub.2 H.sub.4 OCOCH.sub.3                                                            yellow                                      80                                                                                  ##STR98##        H  2 C.sub.2 H.sub.4 Cl                                                                     yellow                                      81                                                                                  ##STR99##        H  2 CHCH.sub.2                                                                             yellow                                      82                                                                                  ##STR100##       H  2 C.sub.2 H.sub.4 OCOCH.sub.3                                                            yellow                                      83                                                                                  ##STR101##       CH.sub.3                                                                          2 C.sub.2 H.sub.4 OCOCH.sub.3                                                            yellow                                      __________________________________________________________________________

EXAMPLE 84

0.5 mol of the coupling solution described in Example 1 was subjected to a condensation reaction with 133.5 g (0.5 mol) of 4-(2-chloroethylsulfonyl)-benzoyl chloride at from 0° to 5° C. and at a pH of from 5 to 6. The reaction solution was then clarified by filtration and the dye was isolated by salting out. It is of the formula (free acid) ##STR102## and dyes cotton in a yellow hue.

The dyes of the formula ##STR103## which are shown in Table 6 can be obtained in a similar manner.

                                      TABLE 6                                      __________________________________________________________________________     Ex. no.                                                                            D                 E  m Y       Hue on cotton                               __________________________________________________________________________     85                                                                                  ##STR104##       H  2 C.sub.2 H.sub.4 OCOCH.sub.3                                                            yellow                                      86                                                                                  ##STR105##       H  2 C.sub.2 H.sub.4 OCOCH.sub.3                                                            yellow                                      87                                                                                  ##STR106##       H  2 C.sub.2 H.sub.4 OCOCH.sub.3                                                            yellow                                      88                                                                                  ##STR107##       H  2 C.sub.2 H.sub.4 OCOCH.sub.3                                                            yellow                                      89                                                                                  ##STR108##       CH.sub.3                                                                          2 C.sub.2 H.sub.4 OCOCH.sub.3                                                            yellow                                      90                                                                                  ##STR109##       H  2 CHCH.sub.2                                                                             yellow                                      91                                                                                  ##STR110##       H  2 C.sub.2 H.sub.4 OCOCH.sub.3                                                            yellow                                      92                                                                                  ##STR111##       H  2 C.sub.2 H.sub.4 OCOCH.sub.3                                                            yellow                                      93                                                                                  ##STR112##       H  2 C.sub.2 H.sub.4 OCOCH.sub.3                                                            yellow                                      __________________________________________________________________________

EXAMPLE 94

126.5 g (0.5 mol) of aniline-2,4-disulfonic acid were diazotized in 500 ml of water containing hydrochloric acid, and the product was added to a solution of 183.5 g (0.5 mol) of the compound of the formula ##STR113## in 500 ml of water. The coupling reaction was carried out at from 0° to 50° C. and at a pH of 3 by adding 2 N sodium hydroxide solution. Thereafter, 84.3 g (0.5 mol) of 2,4,6-trifluoro-5-chloropyrimidine were added to the coupling solution and, for condensation, the temperature was kept at from 0° to 5° C. and at a pH from 6 to 7 by adding 2 N sodium hydroxide solution. The resulting dye solution was clarified by filtration and the reactive dye of the formula (free acid) ##STR114## was isolated by spray drying. It dyes cotton in a yellow hue.

The dyes of the formula ##STR115## which are shown in Table 7 can be obtained in a similar manner.

                                      TABLE 7                                      __________________________________________________________________________     Ex. no.                                                                            D                 X                    Hue on cotton                       __________________________________________________________________________      95                                                                                 ##STR116##                                                                                       ##STR117##          yellow                               96                                                                                 ##STR118##                                                                                       ##STR119##          yellow                               97                                                                                 ##STR120##                                                                                       ##STR121##          yellow                               98                                                                                 ##STR122##                                                                                       ##STR123##          yellow                               99                                                                                 ##STR124##                                                                                       ##STR125##          yellow                              100                                                                                 ##STR126##                                                                                       ##STR127##          yellow                              101                                                                                 ##STR128##       COCBrCH.sub.2        yellow                              102                                                                                 ##STR129##                                                                                       ##STR130##          yellow                              103                                                                                 ##STR131##       COCH.sub.2 CH.sub.2 Cl                                                                              yellow                              104                                                                                 ##STR132##                                                                                       ##STR133##          yellow                              105                                                                                 ##STR134##                                                                                       ##STR135##          yellow                              106                                                                                 ##STR136##                                                                                       ##STR137##          yellow                              107                                                                                 ##STR138##                                                                                       ##STR139##          yellow                              108                                                                                 ##STR140##                                                                                       ##STR141##          yellow                              109                                                                                 ##STR142##                                                                                       ##STR143##          yellow                              110                                                                                 ##STR144##                                                                                       ##STR145##          yellow                              __________________________________________________________________________

EXAMPLE 111

25.3 g (0.1 mol) of aniline-2,4-disulfonic acid were diazotized in 100 ml of water containing hydrochloric acid, and a solution of 22.3 g (0.1 mol) of 1-aminonaphthalene-6-sulfonic acid in 100 ml of water was added. The coupling reaction was carried out at from 0° to 50° C. and at a pH of from 3.5 to 4.0 by means of 2 N potassium bicarbonate solution. The resulting azo compound was again diazotized in a solution containing hydrochloric acid, and a suspension of 32.9 g (0.1 mol) of the compound of the formula ##STR146## in 150 ml of water was added. The second coupling reaction was carried out at from 10° to 150° C. and at a pH of 3 to 4. The resulting solution of the disazo dye was cooled to 0°-5° C. and subjected to a condensation reaction at this temperature with 18.5 g (0.1 mol) of cyanuric chloride at a pH of 5.5. Thereafter, the reaction solution was clarified by filtration and reacted with 17.3 g (0.1 mol) of aniline-3-sulfonic acid at from 40° to 45° C. and at a pH of 6. The resulting reactive dye could be isolated by salting out by means of potassium chloride. It is of the formula (free acid) ##STR147## and dyes cotton in a brown hue.

The dyes of the formula ##STR148## which are shown in Table 8 can be obtained in a similar manner.

                  TABLE 8                                                          ______________________________________                                         Ex.                              λ.sub.max                                                                     Hue on                                  no.   D.sup.1       D.sup.2      [nm]  cotton                                  ______________________________________                                         112                                                                                   ##STR149##                                                                                   ##STR150##  476   brown                                   113                                                                                   ##STR151##                                                                                   ##STR152##  477   brown                                   114                                                                                   ##STR153##                                                                                   ##STR154##  481   brown                                   115                                                                                   ##STR155##                                                                                   ##STR156##  480   brown                                   ______________________________________                                    

EXAMPLE 116

26.7 9 (0.1 mol) of 4-toluidine-2,5-disulfonic acid were diazotized in 100 ml of water containing hydrochloric acid, and a suspension of 32.9 g (0.1 mol) of the compound of the formula ##STR157## in 150 ml of water was added. The coupling reaction was carried out at from 0° to 5° C. and at a pH of from 3 to 3.5 by means of 2 N potassium bicarbonate solution. The azo compound formed was again diazotized in a solution containing hydrochloric acid and the product was once again reacted with a suspension of 32.9 g (0.1 mol) of the above coupling component in 150 ml of water. The second coupling reaction was carried out at from 0° to 5° C. and at a pH of from 3.5 to 4. The resulting disazo dye was then subjected to a condensation reaction with 20.3 g (0.11 mol) of cyanuric chloride at a pH of 5.5. After the end of the reaction, the excess cyanuric chloride was filtered off, 17.3 g (0.1 mol) of aniline-3-sulfonic acid were added to the filtrate and the mixture was heated to 40°-450° C. and brought to a pH of 6. The resulting reactive dye was salted out with potassium chloride. It is of the formula (free acid) ##STR158## and dyes cotton in a yellowish brown hue.

The dyes of the formula ##STR159## which are shown in Table 9 can be obtained in a similar manner.

                  TABLE 9                                                          ______________________________________                                         Ex.                        Hue on                                              no.  D                     cotton                                              ______________________________________                                         117                                                                                  ##STR160##           yellowish brown                                     118                                                                                  ##STR161##           brown                                               119                                                                                  ##STR162##           brown                                               120                                                                                  ##STR163##           brown                                               121                                                                                  ##STR164##           brown                                               122                                                                                  ##STR165##           brown                                               123                                                                                  ##STR166##           brown                                               124                                                                                  ##STR167##           yellowish brown                                     ______________________________________                                    

EXAMPLE 125

0.1 mol of the monoazo compound described in Example 116 was diazotized in a solution containing hydrochloric acid at from 0° to 5° C., and a solution of 22.3 g (3.1 mol) of 1-aminonaphthalene-6-sulfonic acid in 100 ml of water was added. The coupling reaction was carried out at a pH of from 3 to 4 by means of 2 N potassium bicarbonate solution. The resulting disazo compound was subjected to a condensation reaction first with 18.4 g (0.1 mol) of cyanuric chloride at a pH of 5.5 and then with 17.3 g (0.1 mol) of aniline-3-sulfonic acid at from 40° to 45° C. and at a pH of 6. The reactive dye of the formula (free acid) ##STR168## was salted out with potassium chloride. It dyes cotton in a brown hue.

The dyes of the formula ##STR169## which are shown in Table 10 can be obtained in a similar manner.

                                      TABLE 10                                     __________________________________________________________________________     Ex.                                          Hue on                            no.                                                                               D                 K          R            cotton                            __________________________________________________________________________     126                                                                                ##STR170##                                                                                       ##STR171##                                                                                ##STR172##  brown                             127                                                                                ##STR173##                                                                                       ##STR174##                                                                                ##STR175##  brown                             128                                                                                ##STR176##                                                                                       ##STR177##                                                                                ##STR178##  brown                             129                                                                                ##STR179##                                                                                       ##STR180##                                                                                ##STR181##  brown                             130                                                                                ##STR182##                                                                                       ##STR183##                                                                                ##STR184##  brown                             131                                                                                ##STR185##                                                                                       ##STR186##                                                                                ##STR187##  brown                             __________________________________________________________________________

EXAMPLE 132

0.1 mol of the disazo dye solution described in Example 111 was subjected to a condensation reaction with 22 g (0.1 mol) of tetrachloropyrimidine at from 30° to 45° C. and at a pH of from 6 to 7. Thereafter, the solution was clarified by filtration and the dye was isolated by spray drying. It is of the formula (free acid) ##STR188## and dyes cotton in a brown hue.

The dyes of the formula

    D.sup.1 --N═N--D.sup.2 --N═N--K--NH--X

which are shown in Table 11 can be obtained in a similar manner.

      Ex.     Hue on no. D.sup.1 D.sup.2 K X cotton              132       ##STR189##       ##STR190##       ##STR191##       ##STR192##       brown       133      ##STR193##       ##STR194##       ##STR195##       ##STR196##       brown       134      ##STR197##       ##STR198##       ##STR199##       ##STR200##       brown       135      ##STR201##       ##STR202##       ##STR203##       ##STR204##       brown       136      ##STR205##       ##STR206##       ##STR207##       ##STR208##       brown       137      ##STR209##       ##STR210##       ##STR211##       ##STR212##       brown       138      ##STR213##       ##STR214##       ##STR215##       ##STR216##       yellowishbrown       139      ##STR217##       ##STR218##       ##STR219##       ##STR220##       yellowishbrown       140      ##STR221##       ##STR222##       ##STR223##       ##STR224##       brown       141      ##STR225##       ##STR226##       ##STR227##       ##STR228##       brown       142      ##STR229##       ##STR230##       ##STR231##       COCH.sub.2 CH.sub.2 Cl brown       143      ##STR232##       ##STR233##       ##STR234##       ##STR235##       brown       144      ##STR236##       ##STR237##       ##STR238##       ##STR239##       brown 

We claim:
 1. A-reactive dye of the formula I ##STR240## where n is 0 or 1,R¹, R² and R³ are identical or different and, independently of one another, are each hydrogen, C₁ -C₄ -alkyl or phenyl, A is C₂ --C₈ -alkylene which may be interrupted by from 1 to 3 oxygen atoms, imino groups or C₁ -C₄ -alkylimino groups, Y is vinyl or a radical of the formula --CH₂ --CH₂ --Q, where Q is a group which can be eliminated under alkaline reaction conditions, D¹ is phenyl or naphthyl, where these radicals may be monosubstituted or polysubstituted by hydroxysulfonyl, carboxyl, C₁ -C₄ -alkoxycarbonyl, cyano, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, halogen, nitro or vinylsulfonyl or monosubstituted by unsubstituted or substituted phenylazo or by unsubstituted or substituted naphthylazo, D² is unsubstituted or substituted phenylene or unsubstituted or substituted naphthylene and Z is a reactive radical,with the proviso that a) n is zero when D¹ is substituted by unsubstituted or substituted phenylazo or by unsubstituted or substituted naphthylazo, and b) the reactive radical Z is not derived from the triazine series when n is zero and D¹ is dihydroxysulfonylphenyl or trihydroxysulfonylnaphthyl.
 2. A reactive dye as claimed in claim 1, whereinn is zero, R¹, R² and R³ are each hydrogen, A is C₂ -C₄ -alkylene which may be interrupted by an oxygen atom and D¹ is phenyl or naphthyl, where these radicals are mono-substituted to trisubstituted by hydroxysulfonyl.
 3. A reactive dye as claimed in claim 1, wherein Z is a radical from the pyrazine, pyrimidine, quinoxaline, triazine, vinylsulfonyl or acryloyl series.
 4. A method of dyeing or printing organic substrates containing hydroxyl groups or nitrogen atoms comprising applying thereto a reactive dye as claimed in claim
 1. 